Aminophthalimides



Patented Feb. 17, 1948 UNITED STATE PATENT} orncr. 1

Harold T. Lacey, Plainfield, and Robert E. Brouillard, Some rville, N.1., assignors to American Cyanamid Company, New York, N. Y., acorporation of Maine No Drawing. Appl it' ation August 3,

Serial N0. 547,987

5 Claims; (01. 260-326) This invention relates to a new series ofsubstituted aminophthalimides, to processes of coloring therewith and toproducts so colored. These new compounds are strongly fluorescent andthereby adapted to a number of diiierent uses.

In recent years fluorescent compounds have attained considerableimportance in advertising, decorations, exhibitions and in stage work.They have been-variously used for blackout signs, on billboards, inplastics on the instrument panels of airplanes, for identification markson vehicles and for other similar purposes.

They have found use in such widely divergent enerations as being admixedwith fertilizer to show distribution through soil; to show thepenedistribution of oil in leather and water-proofing compounds onconcrete; to detect flaws in metal; to locate sources .of water seepagein mines and oil wells; to accelerate the bleaching of oils byultra-violet light; to accelerate the sterilization of fruit juices byultra-violet light; in face creams to screen out harmful ultra-violetrays.

There is therefore an increasing demand for fluorescent materials whichare readily produced f-rom available materials and which have enhancedfluorescent properties. It is a principal object of the presentinvention to provide a new group of fluorescent materials which arereadily produced, fluoresce strongly and are adapted for many purposes.invention to produce fluorescent materials which are particularly usefulin the dyeing of artificial fibers and the natural vegetable and animalflbers to produce new and improved shades and effect.

More specifically, the invention relates to substitutedaminophthalimides of the general formula:

RHN

N-R c N Y 7 I I O R is an alkylol radical, R is hydrogen, an alkyl, oran alkylol radical, and X is either hydrogen or a halogen. I -It will benoted from the-above general formula ,1 tration of biological fluids inbacteria; to show It is also a further object of the that R may bealkylol and R may be alkyl 'ori-:

- The fluorescent materials of the present invenftion may be prepared byany suitable method.

closethe imide. V v Perhaps the simplest method in operation, and themost economical to carry out, is the preferred method in .which anitrophthalic acid is conalkylol radicals. range of equivalents iromwhich these radical's'may be selected is wide.

For example, thealkyl radicals may be methyl, et yl, propyl, butyl, andthe like. Thealkylol radicals maybe such hydroxyalkyl groups asmethylol, ethylol, and the like.

one such procedure is .to prepare a salt of suit.-

able phthalimide'and'? treat the latter with a halide of the radicalwhich is to be attached to the imide nitrogen; Atftjhe' same time, orsubsequently theretothesubstituent may be added to the ...othernitrogenof, an aminophthalimide or a halophthalic acid may be treated with analkylolamine tojorm, an acid amide and an alkylolamine linkage and theproduct may be treated to densed with an aminoaloohol'and the resultantamide is'heated'suficiently to be dehydrated to the nitroimide, thenitro group of which can then be reduced b'yiany known method. The imideso produced may then be treated to substitute in the amino group.

The inventionwill be more fully illustrated in conjunction with'i thefollowing examples which are to be taken as illustrative only and not byway of limitation. All parts are by weight unless otherwise noted. v

monoethanolamine are refluxed for four hours,

or until reaction is complete. The resultant mixture comprises the3-ethylolaminophthalethylolimide in an excess'of monoethanolamine. Thelatter is removed by fractional distillation. The resultant product is ayellow-brown oil which fluoresces orange in ethyl alcohol solution andgreen when dissolved in acetone or hydrocarbon solvents.

Exsmrn 2 A bath is prepared containing 2 parts of 3-ethylolaminophthalethylolimide, obtained as in Example 1, parts ofsodium chloride, onequarter part of lauryl sulfate, and one-quarter partof sodium pyrophosphate in 3500 parts of water. This bath is heatedto180lj and 100 parts of cellulose'acetate aretreatedftherein for one hour.The resultant dyeing is-reddish-yellow in daylight and orange inultra-violet light.

EXAMPLE 3 s-n-hem zammephthezethyzozimide certa n I? V N-ClHlDH C H O 53parts of 3-nitrophthalic acidis slurried in '50 parts of water and 16.8parts ofmonoethanolamine is added. An exothermic reaction results andthe temperature of the m xture goesup to about C. Thereactionmixture'is-then heated to ISO-165 C. until all evolutionoffvvaterv has ceased and for 30 minutes longer. The mixture is thencooled to C. and diluted withliiil parts of alcohol and stirreduntilhomogeneous. This mixture, containing the nitrophthalethylolamide,is then added slowly to a previously boiled and cooled mixture of 94.4parts of iron borings, 2 parts of 5 N -hydrochloric acid and '125'partof water. The addition requiresabout 30 minutes. The mixture is thenrefluxed -for one hour after which the alcohol is removed bydistillation, and

water is added to' restore the original .volume.

The iron slurry is filtered 'hot'and the resultant presscake washed with25 parts of water at C. The filtrate is cooled to 15-20" C.'with'stirring to precipitate the 3-aminophthalethylolimide which isthen removed from the slurry by filtration. 4.12 parts of dried3-aniinophthalethylolimide, so prepared, 2 parts of pyridine and 4 partsof n-heptyl bromide are dissolved in partsof for four hours. The solventisthen removed by steam distillation and the resulting 3-n-heptylaminophthalethylolimide separated from the aqueous layer. Theproductthus obtained is an amber oil which fluoresces-yellow-green inalcohol and bluish-green in acetone, benzene and mineral oil. Y

EXAMPLE 4 A bath similar to that of Example'2 is prepared, substitutingthe dyestufi ofElxample 3 for that of Example 1. Dyeing is carried outon cellulose acetate-producing an even yellow tint in daylightwhich-fluoresces bright yellow-green un U (161' ultra-violet light.

EXAMPLE 5 3-heptylaminophthaloctadecenylimide C7HJ I 4 w i NOlBiHBi \Gsolid melts at 168-170 C.

10.5 parts of 3-nitrophthalic acid is slurried in 25 parts of alcoholand 14 parts of 9-octodecenylamine-1 added thereto. An exothermicreaction results and the temperature of the mixture rises to 80 C. Thealcohol is then boiled of! and the residue heated for 30 minutes at C.The crude 3-nitrophthaloctadecenylimide thus produced is purified byrecrystallization from alcohol. 9.4 parts of recrystallized3-nitrophthaloctadevcenylimide is dissolved in 200 parts of alcohol andthe-solution added to a previously boiled and cooled slurry of 10 partsof ironborings, 0.2 part of 5 N-hydrochloric acid and 25 parts of water.

The mixture is refluxed for 1 hours, filtered hot, and the filtratecooled to precipitate the 3- v aminophthaloctadecenylirnide.

A mixture consisting of 4.1'parts 0f 3-aminophthalocetade- 'cenylimide,1.6 parts of heptylbromide, 1.5 parts of pyridine, and 50 parts oforthodichlorobenzene is refluxed for 4 hours. The solvent is thenremoved by steam distillation and the 3-hepty1-aminophthaloctadecenylimide separated from the I aqueous layer. Theproduct thus obtained is an amber oily solid which fluorescesyellow-green in alcohol and blue in acetone, benzene and mineral oil.

EXAMPLE 6 3-chloro-6-ethylolaminophthdlethylolimide 5 parts of3,6-dichlorophthalic anhydride and 50 parts of monoethanolamine arerefluxed for 6 hours. The excess monoethanolamine is removed bydistillation and the resulting 3-chloro-6-ethylolaminophthalethylolimide purified by recrystallization fromalcohol. After two crystallizations from alcohol the orange amorphous Itfluoresces bright orange in alcohol.

EXAMPLE 7 A dye bath prepared according to Example 2 is made, using thedyestuff whichwas prepared in Example 6. The resultant dye is a levelorange both in daylight and in ultra-violet light.

We claim:

1. As a new composition of matter an aminophthalimide of the generalformula 7| xaminophthalethylolimide.

5 5. As a new position of matter 3-chIoro-6-ethylo1aminophthalethylolimide.

HAROLD T. LACEY. ROBERT E. BROUILLARD.

REFERENCES CITED The following references are of record in the file ofthis patent:

6 UNITED STATES PATENTS Number Name Date 621,319 Bredt Mar. 21, 18991,618,415 Ellis Feb. 22, 1927 1,836,529 Eckert Dec. 15, 1931 OTHERREFERENCES Beilstein, 4th edition, 1'01. 22, page 534 (1935). Beilstein,4th editionsecond supplement, vol.

22, page 668 (1935).

